EP0342159B1 - Composés phtalocyanine solubles dans l'eau, procédé pour leur préparation et leur utilisation - Google Patents

Composés phtalocyanine solubles dans l'eau, procédé pour leur préparation et leur utilisation Download PDF

Info

Publication number
EP0342159B1
EP0342159B1 EP89810338A EP89810338A EP0342159B1 EP 0342159 B1 EP0342159 B1 EP 0342159B1 EP 89810338 A EP89810338 A EP 89810338A EP 89810338 A EP89810338 A EP 89810338A EP 0342159 B1 EP0342159 B1 EP 0342159B1
Authority
EP
European Patent Office
Prior art keywords
formula
carbon atoms
alkyl
compound
radical
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP89810338A
Other languages
German (de)
English (en)
Other versions
EP0342159A1 (fr
Inventor
Rudolf Dr. Schaulin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Novartis AG
Original Assignee
Ciba Geigy AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ciba Geigy AG filed Critical Ciba Geigy AG
Publication of EP0342159A1 publication Critical patent/EP0342159A1/fr
Application granted granted Critical
Publication of EP0342159B1 publication Critical patent/EP0342159B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B56/00—Azo dyes containing other chromophoric systems
    • C09B56/14—Phthalocyanine-azo dyes

Definitions

  • the present invention relates to new water-soluble phthalocyanine compounds, processes for their preparation and their use for dyeing and printing fiber materials, in particular textile fiber materials.
  • the present invention relates to new water-soluble phthalocyanine compounds of the formula in which R1 and R2 are identical or different and each represent hydrogen, hydroxyalkyl having 2 or 3 carbon atoms, carboxyalkyl having 1 to 3 carbon atoms in the alkyl part or phenyl, or R1 and R2 together with the nitrogen atom mean a heterocyclic ring with optionally further heteroatoms, R3 is hydrogen or methyl, R4 is hydrogen, alkyl or alkoxy each having 1 to 5 carbon atoms, -NHCOR6, where R6 is alkyl or hydroxyalkyl each having 1 to 3 carbon atoms or optionally substituted phenyl, or sulfo, Me is a coordinatively bonded metal atom, Pc a (a + b + c) -valent phthalocyanine residue, n is 1 to 3, A is a monosubstituted phenyl radical, a naphthyl radical, a radical of the formula wherein
  • the substituents R1 and R2 which are the same or different, have the meaning hydrogen, hydroxyalkyl having 2 to 5 carbon atoms, such as hydroxyethyl, hydroxy-n-propyl, hydroxy-n-butyl and hydroxy-n-pentyl, and the corresponding branched hydroxyalkyl radicals; Carboxyalkyl with 1 to 5 carbon atoms in the alkyl part, such as carboxymethyl, carboxyethyl, carboxy-n-propyl, carboxy-n-butyl or carboxy-n-pentyl, and the corresponding carboxyalkyl radicals, the alkyl part of which is branched; or phenyl.
  • Preferred substituents R1 and R2 are hydrogen; Hydroxyethyl or carboxyalkyl having 1 or 2 carbon atoms in the alkyl radical (-CH2COOH, -CH2CH2COOH) or phenyl, with a particularly preferred combination of one of the substituents R1 or R2 being hydrogen and the other one of the stated substituents.
  • Form R1 and R2 together with the nitrogen atom to which they are attached, a heterocyclic ring, it is preferably saturated heterocyclic 5- or 6-rings, which may contain nitrogen, sulfur and / or oxygen atoms as further heteroatoms.
  • heterocyclic radicals -NR1R2 are therefore pyrrolidino, piperidino, pipecolino, morpholino, thiomorpholino or piperazino, pyrrolidino, piperidino, morpholino and thiomorpholino being preferred.
  • R3 is methyl or preferably hydrogen.
  • C1-C5-alkyl for R4 in the compounds of formula (1) are, for example: methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl or isopentyl.
  • C1-C5-alkoxy for R4 for example: methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentoxy or isopentoxy.
  • the alkoxy radicals mentioned having 1 to 3 carbon atoms, in particular methoxy, are preferred.
  • -NHCOR6 for R4 in the compounds of formula (1) are, for example, substituents such as -NHCOCH3, -NHCOCH2CH3, -NHCOCH2CH2CH3, -NHCOCH2OH, -NHCOCH2CH2OH, -NHCOCH2CH2CH2OH or wherein the phenyl ring can be optionally substituted, for example with methyl or halogen.
  • Preferred substituents -NHCOR6 are -NHCOCH3, -NHCOCH2OH or -NHCOC6H5.
  • the meaning sulfo in the substituent R4 includes both the free acid form (-SO3H) and the salt form, alkali metal salts (Li, Na, K) or ammonium salts being particularly suitable.
  • the radical A is one with the substituents alkyl or alkoxy each having 1 to 5, preferably 1 to 3, carbon atoms, the individual substituents being those as indicated for R4; further substituents can be hydroxyl, carboxyl or sulfo.
  • A can have one or more of the substituents mentioned for A as the phenyl radical, e.g. 1 to 4, preferably 1 or 2, contain.
  • Me is a coordinatively bonded metal atom, for example an iron, cobalt, nickel and in particular a copper atom.
  • Pc is the short form for an (a + b + c) -valent phthalocyanine residue.
  • the index a preferably has an (average) value of 1 to 1.2 and particularly preferably the value 1; the index b preferably has an (average) value of 0.5 to 1 and the index c preferably has an (average) value of 1 to 1.2.
  • Preferred compounds of the formula (1) are those in which R1 and R2 are identical or different and are each hydrogen, hydroxyethyl or carboxyalkyl having 1 or 2 carbon atoms in the alkyl radical or phenyl, or R1 and R2 together with the nitrogen atom are a heterocyclic 5- or 6 -membered ring, which may contain nitrogen, sulfur and / or oxygen atoms as further heteroatoms, R4 alkyl or alkoxy each having 1 to 3 carbon atoms, -NHCOCH3, -NHCOCH2OH, -NHCOC6H5 or sulfo and Me a coordinatively bound iron, Cobalt, nickel and in particular copper atom, and Pc, R3, a, b, c and n have the meanings given.
  • Particularly preferred compounds of the formula (1) correspond to the formula wherein R1 and R2 are the same or different and are each hydrogen, hydroxyethyl or carboxyalkyl having 1 or 2 carbon atoms in the alkyl radical or phenyl, or R1 and R2 together with the nitrogen atom represent a heterocyclic 5- or 6-membered ring, which are further heteroatoms May contain nitrogen, sulfur and / or oxygen atoms, R4 alkyl or alkoxy each having 1 to 3 carbon atoms, -NHCOCH3, -NHCOCH2OH, -NHCOC6H5 or sulfo, R5 alkyl or alkoxy having 1 to 3 carbon atoms, as indicated for example for R4 are, hydroxyl, carboxyl or sulfo, and Pc, R3, a, b, c and n have the meanings given.
  • R7 is alkyl having 1 to 4 carbon atoms
  • R8 -CN is alkyl having 1 to 4 carbon atoms
  • R8 -CN is alkyl having 1 to 4 carbon atoms
  • R8 -CN is alkyl having 1 to 4 carbon atoms
  • R8 -CN is alkyl having 1 to 4 carbon atoms
  • R8 -CN is alkyl having 1 to 4 carbon atoms
  • R8 -CN is -CONH2 or -CH2SO3H
  • p is 1 to 4
  • R1, R2, R3, R4, R5, a, b, c and n have the meanings given.
  • the process for the preparation of the compounds of the formula (1) - and this is a further subject of the present invention - is characterized in that metal phthalocyanine sulfochlorides of the formula wherein Me is a coordinatively bound metal atom, x 2.5 to 4, y 0 to 1.5 and the sum of (x + y) 2.5 to 4, preferably 2.5 to 3, with compounds which are primary or secondary Have amino groups, the formulas and (8) HNR1R2, wherein R1, R2, R3, R4, A, Me, Pc and n have the meanings given under formula (1), reacted (condensed) in an aqueous medium at temperatures from 0 to 100 ° C. while maintaining a pH value of 5 to 10 and then optionally hydrolyzed with acid or alkaline.
  • the process according to the invention is preferably carried out at 0 to 40 ° C. and a pH in the range from 5 to 8.
  • Nitrogen-containing compounds such as e.g. Pyridine, nicotinic acid or imidazole are suitable.
  • the compounds of the formulas (7) and (8) can be reacted simultaneously or in succession with the phthalocyanine sulfochlorides of the formula (6), usually first with the azo dyes of the formula (7) containing amino groups and then with the amines of the formula (8 ) is implemented. They are used in (b) or (c) molar amounts based on the compound of the formula (6), preferably also in 0.1 to 1-fold molar excess.
  • the alkaline hydrolysis can be carried out with alkali metal hydroxides, carbonates or bicarbonates or ammonia or amines, and the acidic hydrolysis with mineral acids, in particular hydrochloric or sulfuric acid.
  • An alternative production process for the preparation of the compounds of formula (1) is the phthalocyanine sulfochlorides of the formula wherein x is 2.5 to 4, y is 0 to 1.5 and the sum of x + y is 2.5 to 4, preferably 2.5 to 3, simultaneously or in succession with amines of the formulas and (8) HNR1R2, wherein R9 is a protective group, for example acetyl, and R1, R2, R3, R4, Me, Pc and n have the meanings given, in an aqueous medium at temperatures from 0 to 100 ° C while maintaining a pH of 5 to 10 , then splits off the protective group, diazotizes the resulting amino group and then couples the diazo compound to a coupling component A.
  • the phthalocyanine sulfochlorides of the formula (6) used as starting compounds are known to the person skilled in the art or can be prepared by processes known per se (reaction of the metal phthalocyanine with chlorosulfonic acid and / or thionyl chloride at elevated temperature) (see, for example, K. Venkataraman, The Chemistry of Synthetic Dyes , Vol. V, p. 261 (1971), Academic Press, New York / London: FM Moser, AL Thomas, The phthalocyanines, Vol. II, pp. 20-22, CRC Press; 1983).
  • the compounds of formula (7) are also known, generally yellow azo dyes with a free primary or secondary amino group.
  • the amino compounds of the formulas (8) and (9) are generally known and easily accessible.
  • Another object of the present invention is the use of the phthalocyanine compounds of the formula (1), optionally also mixtures of these compounds, for dyeing or printing nitrogen-containing and in particular hydroxyl-containing fiber materials.
  • phthalocyanine compounds (phthalocyanine azo dyes) of the formula (1) according to the invention are therefore suitable for dyeing and printing nitrogen-containing or, in particular, cellulosic fiber materials, preferably textile fiber materials, made of silk, wool or synthetic polyamides, and preferably from cellulosic fibers such as rayon , Cotton or hemp.
  • direct dyes C.I. direct dyes
  • Textile fiber materials made from mixed fibers e.g. from wool / cotton, polyamide / cotton, polyacrylic / cotton or in particular polyester / cotton mixed fibers can be dyed by a single bath dyeing process and in the presence of dyes for the other types of fibers.
  • the textile fiber materials can be in a wide variety of processing states, e.g. as fiber, yarn, woven or knitted fabric.
  • leather and paper can also be dyed with compounds (dyes) of the formula (1) according to the invention.
  • Level dyeings are obtained in brilliant green shades with good general fastness properties, in particular good fastness to rubbing, wet, wet rubbing, sweat and light. If necessary, the wet fastness properties, in particular the wash fastness, of the direct dyeings and prints obtained can be significantly improved by post-treatment with so-called fixing agents.
  • the dyes of the formula (1) according to the invention can be easily combined with other dyes, in particular disperse dyes.
  • the dyes according to the invention have sufficient high-temperature stability and can thus be used under the dyeing conditions for polyester fibers, i.e. dye at temperatures in the range from about 100 to 150 ° C., preferably from 110 to 130 ° C., from an aqueous liquor and at a pH from 4 to 7.5, preferably 5 to 7.
  • the dyeing of textile mixed fibers e.g. those made of polyester and cellulose fibers
  • the dyeing of textile mixed fibers significantly simplify.
  • the usual dyeing of each type of fiber in a fiber blend in a separate operation using different dyeing conditions is no longer necessary.
  • the compounds of formula (1) according to the invention are also suitable for the production of aqueous inks for ink-jet printing.
  • phthalocyanine dyes which differ from the dyes according to the invention with regard to the lack of at least one substituent of the phthalocyanine radical.
  • Parts and percentages are by weight unless otherwise specified. Parts by weight and parts by volume are related in the same way as kilograms and liters. The temperatures are given in degrees Celsius.
  • Example 1 14.6 parts of copper phthalocyanine sulfochloride (with an average number of 2.5 sulfochloride groups in the molecule) are mixed in 500 parts of water. 12 parts of the compound of the formula are added to this suspension and 1 part pyridine. The reaction mixture is stirred while maintaining the pH at 5.5 with 1N ammonium hydroxide solution for 4 hours at 20 to 25 ° C, then 2 hours at 30 to 35 ° C and finally 2 hours at 40 to 45 ° C. finally the pH is adjusted to 8 with 1N ammonium hydroxide solution and the mixture is stirred for a further hour at 40 to 45 ° C. About 70 parts of 1N ammonium hydroxide solution are used for this.
  • the dye formed is then precipitated with 60 parts of sodium chloride, filtered off and washed with 10% aqueous sodium chloride solution.
  • the filter residue is slurried with hot ethanol, filtered again and washed with hot ethanol until the filtrate is colorless.
  • the dyes of the formulas can also be used in a similar manner and produce.
  • Example 2 14.6 parts of copper phthalocyanine sulfochloride (with an average number of 2.5 sulfochloride groups in the molecule) are stirred in 500 parts of water. 12 parts of the compound of the formula are added to this suspension and 1 part pyridine. The reaction mixture is stirred while maintaining the pH at 7-7.5 with 1N ammonium hydroxide solution for 4 hours at 0 to 5 ° C, then for 2 hours at 20 to 25 ° C and finally for 2 hours at 35 to 40 ° C. The pH is then adjusted to 8 with 1N ammonium hydroxide solution and the mixture is stirred at 40 to 45 ° C. for a further hour. About 70 parts of 1N ammonium hydroxide solution are used for this.
  • the dye formed is then precipitated with 60 parts of sodium chloride, filtered off and washed with 10% aqueous sodium chloride solution.
  • the filter residue is slurried with hot ethanol, filtered again and washed with hot ethanol until the filtrate is colorless.
  • Example 3 43.6 parts of a copper phthalocyanine sulfochloride, which contains an average of about 1.7 sulfochloride groups and about 1.0 sulfonic acid groups per molecule, are suspended in 400 parts of ice water. A solution of 21 parts of the monoazo dye 3-sulfo-2'-acetamido-4'-amino-azobenzene (sodium salt) in 350 parts of ice water and 1.0 part of pyridine is added to this suspension. The reaction mixture is stirred with 1N ammonium hydroxide solution for 4 hours at 0 to 5 ° C, then 2 hours at 20 to 25 ° C and finally 2 hours at 35 to 40 ° C while maintaining the pH at 7.5-8.0 . finally the pH is adjusted to 8 with 1N ammonium hydroxide solution and stirred for a further hour at 40 to 45 ° C. About 70 parts of 1N ammonium hydroxide solution are used for this.
  • the dye formed is then precipitated with sodium chloride, filtered off and washed with aqueous sodium chloride solution.
  • the filter residue is slurried with hot ethanol, filtered again and washed with hot ethanol until the filtrate is colorless.
  • Example 4 23.1 parts of copper phthalocyanine base (sodium salt), about 1.1 sulfonic acid groups, about 0.7 -SO2NH2 groups and about 1.1 groups of the formula per molecule contains (prepared in a manner known per se by sulfochlorination of copper phthalocyanine and subsequent reaction with ammonia and 3-aminoacetanilide, followed by the splitting off of the acetyl protective group), are added to a solution of 2 parts of sodium nitrite in 200 parts of water. After adding 100 parts of ice, a solution of 14 parts of 30% strength hydrochloric acid in 50 parts of ice water is added dropwise at 0 to 2 ° C. with stirring.
  • the suspension of the diazonium salt is then added dropwise at 0 to 4 ° C. to a solution of 6.6 parts of 6-hydroxy-3-carbamoyl-4-methyl-1-ethylpyrid-2-one in 200 parts of ice water.
  • the pH of the reaction mixture is kept at 9 to 9.5 by adding 30% sodium hydroxide solution.
  • sodium chloride is added to the reaction solution, the salted-out dye is filtered off, washed with sodium chloride solution and dried.
  • the dye of the formula is obtained which colors cellulose materials and leather in brilliant shades of green with good lightfastness.
  • Examples 5 to 10 The following dyes can be prepared analogously as described in Examples 1 to 3, and each dye cellulose materials and leather in brilliant green shades with good general fastness properties:
  • a fiber mixture of polyester and cotton 10 parts are placed in a dye bath at approx. 50 ° C, which contains 200 parts of water, a dye mixture consisting of 0.05 parts of C.I. Disperse Yellow 99, 0.5 parts C.I. Disperse Blue 60 and 0.2 part of the dye according to Example 3, 0.4 part of ammonium sulfate and 0.2 part of an anionic dispersing agent (e.g. formaldehyde condensation product of naphthalenesulfonic acid).
  • an anionic dispersing agent e.g. formaldehyde condensation product of naphthalenesulfonic acid.
  • the dyeing is continued for a further 45 minutes at 130 ° C., the dye bath is then cooled to approximately 80 ° C. in the course of 30 minutes and left at this temperature for a further 45 minutes.
  • the stain is then rinsed thoroughly with cold water and dried.
  • the procedure is as described in dyeing instructions 1 or 2, but after the dyeing process has been completed, the cold-rinsed dyeing is placed in a fresh bath at about 30 ° C. which contains 200 parts of water and 0.2-0.6 parts of a cationic aftertreatment agent (amine -Formaldehyde-dicyandiamide condensation product or preparation based on dicyandiamide and diethylenetriamine).
  • a cationic aftertreatment agent amine -Formaldehyde-dicyandiamide condensation product or preparation based on dicyandiamide and diethylenetriamine.
  • the procedure is as described in dyeing instructions 1 or 2, but after the dyeing process has been completed, the cold-rinsed dyeing is placed in a fresh bath at about 25 ° C. which contains 200 parts of water, 1 part of Glauber's salt and 0.6 part of a fiber-reactive cationic aftertreatment agent Contains base of N-methyldialkylamine and epichlorohydrin. The temperature is raised to 40 ° C. in the course of 15 minutes, 0.8 part of 30% strength sodium hydroxide solution is added and the dyeing is treated at 40 ° C. for a further 45 minutes. The dyeing is then rinsed hot and dried; it has improved wet fastness properties.

Claims (13)

  1. Procédé de préparation de composés de formule :
    Figure imgb0090
     dans laquelle :
    R₁ et R₂   sont identiques ou différents l'un de l'autre et représentent chacun un atome d'hydrogène, un groupe hydroxyalkyle comportant 2 ou 3 atomes de carbone, un groupe carboxyalkyle comportant de 1 à 3 atomes de carbone dans le fragment alkyle ou un groupe phényle, ou bien
    R₁ et R₂   forment conjointement avec l'atome d'azote un noyau hétérocycle comportant éventuellement d'autres hétéroatomes,
    R₃   représente un atome d'hydrogène ou un groupe méthyle,
    R₄   représente un atome d'hydrogène, un groupe alkyle ou alcoxy comportant dans chaque cas de 1 à 5 atomes de carbone, un groupe -NHCOR₆, où R₆ représente un groupe alkyle ou hydroxyalkyle comportant dans chaque cas de 1 à 3 atomes de carbone ou un groupe phényle éventuellement substitué, ou un groupe sulfo,
    Me   représente un atome de métal lié par coordinence,
    Pc   représente un reste de phtalocyanine de valence (a+b+c),
    n   vaut de 1 à 3,
    A   représente un groupe phényle monosubstitué, un groupe naphtyle, un groupe de formule :
    Figure imgb0091
     dans laquelle :
    R₇   représente un groupe alkyle comportant de 1 à 4 atomes de carbone, et
    R₈   représente un groupe -CN, -CONH₂ ou -CH₂SO₃H,
    ou un groupe de formule :
    Figure imgb0092
     dans laquelle :
    R₁₀   représente un groupe -NH₂, -COOH, méthyle ou éthyle, et
    R₁₁   représente un groupe 1- ou 2-naphtyle, éventuellement substitué par un ou des groupes sulfo, ou un groupe phényle non-substitué ou portant des substituants alkyle en C₁₋₃, alcoxy en C₁₋₃, chloro, sulfo, méthylsulfonyle, acétylamino, hydroxy et/ou carboxy,
    a   vaut de 1 à 1,5,
    b   vaut de 1 à 2, et
    c   vaut de 1 à 2,
    la somme (a+b+c) valant de 2,5 à 4,
    caractérisé en ce que l'on fait réagir un sulfochlorure de phtalocyanine de métal, de formule :
    Figure imgb0093
     dans laquelle :
    x   vaut de 2,5 à 4,
    y   vaut de 0 à 1,5 et la somme (x+y) vaut de 2,5 à 4, de préférence de 2,5 à 3,
    simultanément ou successivement, avec des amines de formule :
    Figure imgb0094
     et (8) HNR₁R₂,
    dans lesquelles :
    R₁, R₂, R₃, R₄, A, Me, Pc et n ont les significations indiquées ci-dessus,
    en milieu aqueux et à des températures de 0 à 100°C, tout en maintenant le pH à une valeur de 5 à 10, et en ce que l'on effectue ensuite, éventuellement, une hydrolyse avec un acide ou un composé alcalin.
  2. Procédé conforme à la revendication 1, caractérisé en ce que :
    R₁ et R₂   sont identiques ou différents l'un de l'autre et représentent chacun un atome d'hydrogène, un groupe hydroxyéthyle, un groupe carboxyalkyle comportant 1 ou 2 atomes de carbone dans le groupe alkyle, ou un groupe phényle, ou bien
    R₁ et R₂   forment, avec l'atome d'azote, un noyau hétérocyclique à 5 ou 6 chaînons, qui peut comporter, comme autres hétéroatomes, des atomes d'azote, de soufre et/ou d'oxygène,
    R₄   représente un groupe alkyle ou alcoxy comportant dans chaque cas de 1 à 3 atomes de carbone, un groupe -NHCOCH₃, -NHCOCH₂OH, ou -NHCOC₆H₅, ou encore un groupe sulfo,
    Me   représente un atome de fer, de cobalt, de nickel ou en particulier de cuivre, lié par coordinence, et
    Pc, R₃, a, b, c et n ont les significations indiquées dans la revendication 1.
  3. Procédé conforme à la revendication 1 ou 2, caractérisé en ce qu'il correspond à la formule :
    Figure imgb0095
     dans laquelle :
    R₁ et R₂   sont identiques ou différents l'un de l'autre et représentent chacun un atome d'hydrogène, un groupe hydroxyéthyle, un groupe carboxyalkyle comportant 1 ou 2 atomes de carbone dans le groupe alkyle, ou un groupe phényle, ou bien
    R₁ et R₂   forment, avec l'atome d'azote, un noyau hétérocyclique à 5 ou 6 chaînons, qui peut comporter, comme autres hétéroatomes, des atomes d'azote, de soufre et/ou d'oxygène,
    R₄   représente un groupe alkyle ou alcoxy comportant dans chaque cas de 1 à 3 atomes de carbone, un groupe -NHCOCH₃, -NHCOCH₂OH, ou -NHCOC₆H₅, ou encore un groupe sulfo,
    R₅   représente un groupe alkyle ou alcoxy comportant de 1 à 3 atomes de carbone, hydroxyle, carboxyle ou sulfo, et
    Pc, R₃, a, b, c et n ont les significations déjà indiquées.
  4. Procédé conforme à la revendication 1 ou 2, pour la préparation de composés de formules :
    Figure imgb0096
     et
    Figure imgb0097
     dans lesquelles :
    R₇   représente un groupe alkyle comportant de 1 à 4 atomes de carbone,
    R₈   représente -CN, -CONH₂ ou -CH₂SO₃H,
    p   vaut de 1 à 4, et
    R₁, R₂, R₃, R₄, R₅, a, b, c, et n ont les significations indiquées dans la revendication 1.
  5. Procédé conforme à l'une des revendications 1 à 4, caractérisé en ce que a et c valent de 1 à 1,2, indépendamment l'un de l'autre, et en ce que b vaut de 0,5 à 1.
  6. Procédé conforme à la revendication 1, pour la préparation de composés de formule :
    Figure imgb0098
  7. Procédé conforme à la revendication 1, pour la préparation de composés de formule :
    Figure imgb0099
  8. Procédé conforme à la revendication 1, pour la préparation de composés de formule :
    Figure imgb0100
  9. Procédé de préparation de composés de formule 1, conforme à la revendication 1, caractérisé en ce que l'on fait réagir un sulfochlorure de phtalocyanine de métal, de formule :
    Figure imgb0101
     dans laquelle :
    x   vaut de 2,5 à 4,
    y   vaut de 0 à 1,5 et la somme (x+y) vaut de 2,5 à 4, de préférence de 2,5 à 3,
    simultanément ou successivement, avec des amines de formules :
    Figure imgb0102
     et (8) HNR₁R₂,
    dans lesquelles :
    R₉   représente un groupe protecteur, par exemple acétyle, et
    R₁, R₂, R₃, R₄, Me, Pc et n   ont les significations indiquées dans la revendication 1,
    en milieu aqueux et à des températures de 0 à 100°C, tout en maintenant le pH à une valeur de 5 à 10, puis on sépare le groupe protecteur, on diazote le groupe amino formé et l'on fait ensuite copuler le composé diazo sur un copulant A.
  10. Utilisation des colorants préparés selon un procédé conforme aux revendications 1 à 9, pour la teinture et l'impression te matériaux fibreux azotés et en particulier de matériaux fibreux cellulosiques.
  11. Utilisation conforme à la revendication 10, caractérisée en ce que l'on teint des mélanges de fibres constitués de fibres synthétiques et de matériaux fibreux cellulosiques, en particulier des tissus mélangés polyester/ coton, en présence d'un colorant dispersé pour fibres de polyester, dans les conditions de teinture pour fibres de polyester.
  12. Procédé de teinture de tissus mélangés polyester/coton avec des colorants dispersés et des colorants directs, caractérisé en ce que l'on utilise, en un procédé en une seule étape et à un seul bain, des colorants de formule (1) conformes à la revendication 1, en plus de colorants dispersés, et en ce que l'on effectue la teinture en bain aqueux à des températures situées dans l'intervalle allant de 100 à 150°C et de préférence de 120 à 130°C, et à un pH situé entre 4 et 7,5.
EP89810338A 1988-05-11 1989-05-01 Composés phtalocyanine solubles dans l'eau, procédé pour leur préparation et leur utilisation Expired - Lifetime EP0342159B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH178688 1988-05-11
CH1786/88 1988-05-11

Publications (2)

Publication Number Publication Date
EP0342159A1 EP0342159A1 (fr) 1989-11-15
EP0342159B1 true EP0342159B1 (fr) 1993-09-01

Family

ID=4218568

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89810338A Expired - Lifetime EP0342159B1 (fr) 1988-05-11 1989-05-01 Composés phtalocyanine solubles dans l'eau, procédé pour leur préparation et leur utilisation

Country Status (8)

Country Link
US (1) US4992532A (fr)
EP (1) EP0342159B1 (fr)
JP (1) JPH0218462A (fr)
KR (1) KR900018120A (fr)
BR (1) BR8902191A (fr)
DE (1) DE58905415D1 (fr)
ES (1) ES2058591T3 (fr)
MX (1) MX15982A (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2725948B2 (ja) * 1992-06-11 1998-03-11 シーケーディ株式会社 シールリング
FR2866805B1 (fr) * 2004-02-27 2007-06-29 Oreal Composition comprenant un colorant mixte a base d'au moins un chromophore de type azo ou tri-(hetero)aryle methane, procede de coloration et colorants mixtes

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB763343A (en) * 1952-07-31 1956-12-12 Durand & Huguenin Ag New water-soluble mordant azophthalocyanine dyestuffs and process for making them
BE521833A (fr) * 1952-07-31
CH423407A (de) * 1961-08-16 1966-10-31 Durand & Huguenin Ag Verfahren zum Färben von Oxydschichten
DE1176300B (de) * 1961-09-28 1964-08-20 Siegle & Co G M B H Farbenabri Verfahren zur Herstellung von basischen Phthalocyaninfarbstoffen
FR1530577A (fr) * 1967-05-17 1968-06-28 Ugine Kuhlmann Nouveaux colorants azoïques solubles dérivés de phtalocyanine
US3625936A (en) * 1967-08-12 1971-12-07 Hoechst Ag Azophthalocyanine dyestuffs and process for preparing them
DE2712367C3 (de) * 1977-03-22 1980-04-24 Hoechst Ag, 6000 Frankfurt Verfahren zur Herstellung von Azofarbstoffen auf cellulosehaltigen oder aus Cellulose bestehenden Fasermaterialien
DE3009788A1 (de) * 1980-03-14 1981-10-01 Basf Ag, 6700 Ludwigshafen Wasserloesliche nickelphtalocyaninazofarbstoffe
US4602084A (en) * 1982-07-19 1986-07-22 Ciba-Geigy Corporation Monoazo dyes containing a 4-substituted-2-azo-1,1'-diphenylsulfone component
JPS6187759A (ja) * 1984-09-06 1986-05-06 Nippon Kayaku Co Ltd 水溶性フタロシアニン化合物を用いる基材表面皮膜の着色法

Also Published As

Publication number Publication date
KR900018120A (ko) 1990-12-20
ES2058591T3 (es) 1994-11-01
EP0342159A1 (fr) 1989-11-15
BR8902191A (pt) 1990-01-02
JPH0218462A (ja) 1990-01-22
DE58905415D1 (de) 1993-10-07
US4992532A (en) 1991-02-12
MX15982A (es) 1993-09-01

Similar Documents

Publication Publication Date Title
EP0465420B1 (fr) Colorants azoiques
DE3512630A1 (de) Verfahren zum faerben oder bedrucken von cellulosefasern oder cellulosemischfasern
DE1544446B2 (de) Von Sulfon- und Carbonsäuregruppen freie wasserunlösliche Monoazofarbstoffe und Verfahren zu ihrer Herstellung
DE2745024C2 (fr)
EP0073178B1 (fr) Colorants réactifs, leur préparation et leur utilisation
EP0342159B1 (fr) Composés phtalocyanine solubles dans l'eau, procédé pour leur préparation et leur utilisation
EP0718374B1 (fr) Mélanges de colorants contenant des colorants complexes de chrome 1:2 et colorants complexes de chrome 1:2
DE1226728B (de) Verfahren zur Herstellung von metallhaltigen Reaktivfarbstoffen
EP0342158B1 (fr) Composés phtalocyanine solubles dans l'eau, procédé pour leur préparation et leur utilisation
EP0265828B1 (fr) Composés disazoiques solubles dans l'eau, leur procédé de préparation et leur utilisation comme colorants
EP0776948B1 (fr) Mélanges de colorants de monoazopyridone
DE3629574A1 (de) Wasserloesliche disazoverbindungen, verfahren zu ihrer herstellung und ihre verwendung als farbstoffe
EP0889098A2 (fr) Colorants azoiques, procédépour leur préparation et leur utilisation
EP1088858B1 (fr) Colorants réactifs contenant un groupe chromophore de type formazane et un groupe chromophore de type monoazoique, procédé pour leur préparation et leur utilisation
DE1904112C3 (de) Faserreaktive, schwermetallhaltige Formazanfarbstoffe, Verfahren zu ihrer Herstellung und deren Verwendung zum Färben oder Bedrucken von Textilmaterial
CH628919A5 (de) Verfahren zur herstellung von azofarbstoffen.
EP0230909B1 (fr) Composés azoiques solubles dans l'eau, procédé pour leur préparation et leur utilisation comme colorants
DE2934247A1 (de) Verfahren zur veredlung von faserigen materialien
EP0457729B1 (fr) Colorants azoiques, procédé pour leur préparation et leur utilisation
DE2520123A1 (de) Verfahren zur herstellung von formazanmetallkomplexfarbstoffen
EP0690103A1 (fr) Colorants azoiques, procédé pour leur préparation et leur utilisation
EP0726297A1 (fr) Mélanges de colorants et leur utilisation
DE1298661B (de) Verfahren zur Herstellung in Wasser schwer loeslicher Dispersionsfarbstoffe
DE3400107C2 (fr)
EP0230210B1 (fr) Colorants réactifs, leur préparation et leur utilisation

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19890503

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE CH DE ES FR GB IT LI

17Q First examination report despatched

Effective date: 19920217

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE CH DE ES FR GB IT LI

ET Fr: translation filed
REF Corresponds to:

Ref document number: 58905415

Country of ref document: DE

Date of ref document: 19931007

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19931027

ITF It: translation for a ep patent filed

Owner name: SOCIETA' ITALIANA BREVETTI S.P.A.

ITTA It: last paid annual fee
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2058591

Country of ref document: ES

Kind code of ref document: T3

REG Reference to a national code

Ref country code: CH

Ref legal event code: PUE

Owner name: CIBA-GEIGY AG TRANSFER- CIBA SC HOLDING AG

BECN Be: change of holder's name

Effective date: 19961129

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19970319

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19970411

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19970421

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19970423

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 19970513

Year of fee payment: 9

REG Reference to a national code

Ref country code: CH

Ref legal event code: PFA

Free format text: CIBA SC HOLDING AG TRANSFER- CIBA SPECIALTY CHEMICALS HOLDING INC.

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19970703

Year of fee payment: 9

REG Reference to a national code

Ref country code: FR

Ref legal event code: CD

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980501

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980504

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980531

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980531

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980531

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980531

REG Reference to a national code

Ref country code: ES

Ref legal event code: PC2A

BERE Be: lapsed

Owner name: CIBA SPECIALTY CHEMICALS HOLDING INC.

Effective date: 19980531

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19980501

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990302

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20010503

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050501